Methods of combating mites and fungi



United States Patent F 3,096,237 METHODS OF COMBATING MITES AND FUNGI Engelbert Kiihle and Ferdinand Grewe, Cologne-Staminheim, Giinter Unterstenhofer, Opladen, Martin Boness,

Bergisch-Neukirchen, and Richard Wegler, Leverkusen,

Germany, assignors t0 Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed May 11, 1960, Ser. No. 28,215

Claims priority, application Germany May 13, 1959 8 Claims. (Cl. 16730) The present invention relates to and has as its objects pest control agents with outstanding biological activities against insects, especially mites, as well as against phytopathogenic fungi. This invention furthermore relates to a method of combating the aforementioned pests with these compounds.

Generally the compounds to which this invention is related may be represented by the following formula In the above formula R may denote an optionally substituted alkoxy, aroxy, aralkoxy radical, the radical of a heterocyclic alcohol, an aliphatic, aromatic or heterocyclic amino group which may be further substituted at the nitrogen atom, a hydroxylamine radical, an optionally substituted hydrazine radical or a sulfonic acid amide radical; R stands for hydrogen, an alkyl radical or, together with R for an additional C--C-bond; moreover, R may denote hydrogen; R represents an alkyl radical, an optionally substituted aryl, cycloalkyl or heterocyclic radical; R and R may be identical or different and stand for hydrogen, an alkyl, aryl, aralkyl, heterocyclic radical or for the group wherein R and R may denote hydrogen, an alkyl, aryl or acyl radical.

The compounds useful according to the present invention are partially known and if not known may be prepared strictly in accordance with the methods known for the preparation of the known compounds. Thus, the compounds used to this invention are expediently produced according to the following general reaction scheme in which the radicals R to R have the above mentioned significance:

As it is to be seen from the above scheme a suitable ,B-dicarbonyl-compound is reacted with a suitable amine 3,096,237 Patented July 2, 1963 ice or with ammonia and the acrylic derivative eventually is hydrogenated to a saturated compound.

Part of the compounds may be obtained starting from (suitable) diketenes; in case of R of the above formulae being hydrogen. The following scheme may illustrate this way:

I-IN di-ketene Rt R1H R CCHzC/OOH (opt.subst.)

fl-Dodecyla-mino-fl-phenylacrylic acid methyl ester,

fi-Dibutyl-amino-[i-(p-chlorophenyl)-acrylic acid phenyl ester,

fl-Octadodecylamino-fi-(p-nitrophenyl)-acrylic acid dimethyl amide,

fi Dodecylamino-fl-(p-nitrophenyl)-acrylic acid ethyl 1 ester,

fl-Methylamino-B-(o-chlorophenyl)-acrylic acid dodecyl amide, fl-Dodecylamino-fl-(u-naphthyl)-acrylic acid butyl ester, fi-Dodecylamino-d(Z-furyl)-acrylic acid ethyl ester, fi-Dodecylamino-B-(4-pyridyl)-acrylic acid methyl ester, fl-Dodecylamino-fl-(p-nitrophenyl)-propionic acid ethyl ester, s-Dodecylamino-crotonic acid anilide, fl-Dodecylaminocrotonic acid-(3,4-dichlor-anilide), B-Dodecyia-mino-crotonic acid- (o-anisidide) N-(fl-dodecylamino-crotonyl)-benzenesulfonamide, fi-Dibutylamino-crotonic acid dodecylamide,

fiDodecylamino-crotonic acid-(N-methylanilide),

- flMor'pholino-crotonic acid tetradecylamide, p-Octade'cylamino-crotonic acid anilide,

fl-Dibutylar'nino-crotonic acid anilide, fi-Dibutylarnino-butyric acid dodecylamide, fl-Dodecylamino-crotonic acid-(Z-chloroethyl ester), fi-Dodecylamino crotonic acid- (2-phenylhydrazide fl-Methylamino-crotonohydroxamic acid,

fi-Dodecylamino-crotonic acid phenyl ester, fl-(2.4-dichlorophenoxy-acetylhydrazino)-crotonic acid methyl ester,

fl-Dodecylamino-fl-ethylacrylic acid ethyl ester, and the like.

For the pnotection of infested plants or plants to be protected against infestation the above compounds may be used as such, but preferably in combination with 3 suitable inert solvents or diluents of solid or liquid nature. Solid extenders are e.g. chalk, talc, bentonite, clay, fullers earth and the like. Liquid diluents may be of organic solvent nature, but preferably Water. In the Example 4 Ovicidal activity on Tetrzmychus relarius of'fl-dodecylamino-crotonic acid anilide:

latter case the use of emulsifiers or surface active agents 5 may be advantageous. Such aux liary agents are pref- Percent ofhatchedmsects erably polyglycol ethers of aromatic hydroxy compounds Cone. or fatty alcohols. Percent Meal Bean Bee The following examples are given for the purpose of moth bottle moth illustrating the present invention:

0.1 0 0 0 Example 1 0. 03 0 0 7s 0.01 0 100 Fungicidal activity of various B-ammo-fl-aryl-acryhc M03 0 100 100 acid derivatives on Phytophthora infestans on tomatoes:

Degree of infestation in percent with preparations at concentra- Compound tions of OgN-(|J==CHC O1-C2H5 5 33 NHCuHzs CHaO-(E=CHOO2C2H5 0.2 9

NHOIQHM CH3O(|3=CH-C ONHNH-Q 0 0.4

NHO Hfi OH3O-C=OHCONHOH 0 0.6

NHC12H25 N (!J=OHC 0262115 8 20 NHC'rzHzs \O/ C=CHC0zC2H5 7 18 NHC12H25 Control agent 3 7 Control test 100 Example 2 Example 5 Fungicidal action of various fl-amino-fl-arybacrylie acid derivatives on Plasmopara on vine:

Compound Degree 1 o=cn--oozoitn 10 Control agent (captan) 9 Control test 100 1 Of infestation in percent with preparations at concentrations of 0. 0125.

Example 3 Acaricidal activity of various fl-aminocrotonic acid amides on the spider mites Tetranychus telarius (green species) at a concentration of 0.2%:

Percent killed Compound: after 48 hours B-Dodecylamino-crotonic-acid anilide fl-Dodecylamino crotonic acid-(o-chloroanilide) 80 B-Dibutylamino-crotonic-acid-(N methyldodecylamide) 100 fi-Dodecylamino-crotonic-acid-(o-toluidide) 95 fi-Dipropylamiuo-orotonic-acid-d-odecylarnide 100 N-(fi dodecylamino-crotonyl)-benzene-sulfonamide 80 ,8 Di butylarnino-crotonic acid-(N-methyl-octadecylarnide) 100 Fungicidal activity of various fl-aminocrotonic acid and fi-amino-butyric acid derivatives on Phytophthora infestans on tomatoes:

Degree of infestation in percent at concentra- Compound tions of fl-Dodecylamino-crotonic acid anilide 11 22 B-Diisobutylarnino-crotonic acid dodecylamirle 2 2 10 B-Tetradecylamino-crotonic acid anilide 3 19 48 fi-Dgdeoylamino-crotonic acid-(Z-chloroani- 1 1i fl-Dodecylamino-crotonic acid-( oludide).-. 0 fl-Dodecylamino-crotonic acid-(2-anisidide) 1 fl-Dodecylamino-crotonic acid-benzylarnide 0 B-Dodecylamino-crotonic aeid (N-methylan- Example 5-Continued Degree of iniestation in percent at concentra- Compound tions of- B-Dodecylamino-crotonic acid-(2-n1ethoxyethyl-ester) 6 17 29 fi-Dodecylamino-crotonic acid ethanol amide. 1 13 B-Dodecylarnino-crotonic acid (2.6-dimcthylanilide) 24 fl-Dodecylamino-crotonic acid-diphenyl amide 4 29 B-Dodecylamino-crotonic acid-(4-dimethylamino-anilide) 0 30 fi-Dodecylamino-crotouic acid-(Z-carboxymethyl-anilidc) 4 27 35 B-Dodecylamino-crotonic acid-(B-cyanoanilid 6 27 35 B-Dodecylamino-crotonie acid-(4-rhodanic anilide) 41 60 fl-Dodecylamino-crotonic acid-morpholide. 2 15 2-(fl-dodecy1aroino-crotonyl) -aminopyridine 2 35 B-Dodecylamino-crotonic acid-(4-hydroxyani d 3 22 41 B-Dodecylamino-crotonic acid- (zinc salt) fi-Dodeeylamino-crotonic acid hydroxane (manganese salt) 2 fi-Dodecylamino-butyric acid-anilide-.- 14 B-Dodecylamino-butyric aeid-(2-chloro lide) 0.5 3 fl-(N-methyl-dodccylamino)-butyric acid anilide 8 Zineh 3 9 17 22 Control 100 Example 6 The fungicidal activity of various fl-amino-crotonic acid derivatives on Plasmcpara on vine is to be seen from the following table:

wherein R is a member selected from the group consisting of an anilino radical, a phenyl radical and a phenylsulfonyl radical; R is a member selected from the group consisting of methyl and a phenyl radical; and Alk is an alkyl radical having 10 to 18 carbon atoms.

2. The method of claim 1 wherein the active ingredient is ,8 (p-methoXy-phenyl) {3 dodecylamino-acrylic acid phenyl-hydrazide.

3. The method of claim 1 wherein the active ingredient is fl-dodecylamino-crotonic acid anilide.

4. The method of claim 1 wherein the active ingredient is N-(B-dodecylamino-crotonyl)-3-nitro-benzene sulfonamide.

5. A method for combating mites which comprises contacting the mites with an eifective amount of a compound of the formula wherein R is a member selected from the group consisting of an aniline radical, a phenyl radical and a phenylsulfonyl radical; R is a member selected from the group consisting of methyl and a phenyl radical; and Alk is an alkyl radical having 10 to 18 carbon atoms.

6. The method of claim 5 wherein the active ingredient is B-(p-methoxy-phenyl fi dodecylamino-acrylic acid phenyl-hydrazide.

7. The method of claim 5 wherein the active ingredient is fl-dodecylamino-crotonic acid anilide.

8. The method of claim 5 wherein the active ingredient is N-(,B-dodecylamino-crotonyl)-3-nitro-benzene sulfonamide.

References Cited in the file of this patent UNITED STATES PATENTS 2,268,206 Epstein et a1 Dec. 30, 1941 2,273,849 Epstein et al Feb. 24, 1942 2,290,174 Epstein et al. July 21, 1942 2,323,391 Goodman July 6, 1943 2,368,195 Britton et a1 Jan. 30, 1945 2,505,681 Martin et a1 Apr. 25, 1950 2,507,110 Lcekley May 9, 1950 2,588,969 Dickey et a1 Mar. 11, 1952. 2,898,373 Klaui Aug. 14, 1959 2,938,053 Blake et a1. May 24, 1960 2,941,002 Ehrhart et a] June 14, 1960 2,945,883 A-lberti et al July 19, 1960 2,959,518 Uhlenbroek et a1 Nov. 8, 1960 FOREIGN PATENTS 809,286 Great Britain Feb. 18, 1959 OTHER REFERENCES Knott et a1.: Deutsche Chemische Gesellschaft Berichte, vol. 25, pages 768778 (1892). 

1. A METHOD FOR COMBATING FUNGUS INFESTION OF A PLANT WHICH COMPRISES TREATING THE PLANT WITH AN EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA 